Polymerization process employing a modified iron coordination catalyst



United States Patent 3,419,505 POLYMERIZATION PROCESS EMPLOYING AMODIFIED IRON COORDINATION CATALYST William E. Marsico, Dallas, Tex.,assignor to Columbia Carbon Company, New York, N.Y., a corporation ofDelaware No Drawing. Continuation-impart of application Ser. No.400,543, Sept. 30, 1964. This application Aug. 18, 1965, Ser. No.480,787

19 Claims. (Cl. 260-2) ABSTRACT OF THE DISCLOSURE A description isprovided of the preparation of highly active homogeneous ironcoordination catalysts by the interaction of a hydrocarbon solubleferric compound, an aluminum alkyl and a phosphorus ester having atleast one phosphinic hydrogen group. The use of such catalysts isillustrated by the homopolymerization of 1,2-alkylene oxides andconjugated dienes and the interpolymerization of conjugated dienes withalpha-olefins, alpha-unsaturated nitriles or alkylene oxides. 1

This invention relates to a catalytic process for the preparation ofhomopolymers and interpolymers of various polymerizable organicmonomers. This invention also relates to a novel interpolymer produced'by applying the process of this invention to an admixture of aconjugated aliphatic diene and an epoxide.

This application is a continuation-in-part of my copending applicationSer. No. 400,543, filed Sept. 30, 1964, now US. Patent No. 3,340,489,entitled Composition of Matter.

Coordination catalysts prepared by the interaction of iron compoundswith various reducing agents in the presence of triorgano phosphines andphosphites art well known in the prior art. Such compositions have beensuggested for use as catalysts for the preparation of cyclic and linearhomooligorners of lower aliphatic conjugated dienes and low molecularweight cooligomers of these dienes with certain vinyl hydrocarbons;however, they have met with little commercial acceptance as catalystsfor the production of high polymers because of the excessive inductionperiods and reaction times and low yields which accompany their use.

It is an object of this invention to provide a process, utilizingcertain iron coordination catalysts as described below, for producinghigh molecular weight homopolymers and interpolymers of conjugateddienes in high yield and without the disadvantages which havecharacterized prior art processes. More specifically it is an object ofthis invention to prepare polymers of conjugated aliphatic dienes and ofepoxides. It is a further object of this invention to prepareinterpolymers of conjugated aliphatic dienes and of epoxides. It is afurther object of this invention to prepare interpolymers of conjugatedaliphatic dienes and ethylenically unsaturated monomers, particularlythose containing terminal unsaturation. It is yet a further object ofthis invention to prepare novel interpolymers of conjugated aliphaticdienes and epoxides whichare elastomeric and sulfur-curable. It is stillanother object of this invention to prepare interpolymers ofacrylonitrile, butadiene and styrene. It is still yet another object ofthis invention to prepare interpolymers of ethylene, propylene andbutadiene. Further objects and features of advantage will be apparentfrom a consideration of the following detailed description of theinvention.

It has now been found that the above objects can be accomplished by theuse of a novel catalyst composition which is an admixture product of (a)an iron (III) compound, (b) a hydrocarbyl, hydrocanboxy or hydride compound of aluminum, and (c) a phosphorus ester having at least onephosphinic hydrogen atom. By the use of these catalyst compositions inthe practice of the process of the instant invention one obtainsunexpectedly rapid and highly selective production of high molecularweight homopolymers and interpolymers as described below. The use ofthese novel iron coordination compositions in the practice of theprocess of the present invention exhibit catalytic activity which isunexpectedly superior to that possessed by the similar coordinationcatalysts of the prior art. This superiority is manifested by a drasticreduction in reaction time and a multifold increase in high polymerselectivity over that experienced in the low temperature polymerizationof conjugated aliphatic dienes with the prior art catalysts (cf.Examples XV and XVI). This high catalytic activity is furtherdemonstrated by the fact that the catalyst compositions employed in thepractice of the process of the present invention can be used in very lowconcentration to effect the rapid and eflicient produc tion of highmolecular weight alkylene oxide homopoly mers and interpolymers ofalkylene oxides and conjugated dienes. The use of the prior art ironcoordination catalyst compositions have proven ineffective in theinterpolymerization of conjugated dienes and alkylene oxides.

A mode of accomplishing the above objects is to subject the monomers ormixtures of monomers, above-mentioned, to reaction pressures of fromabout 1 atmosphere to about 1,000 atmospheres, and to temperatures offrom about 30 C. to about 300 C. in the presence of the novel catalystsystem mentioned above. It is to be understood that both higher or lowertemperatures and pressures may be employed in the practice of theprocess of the present invention. However, it is seldom necessary tooperate outside the preferred pressure and temperature ranges, which arefrom about 1 atmosphere pressure to about 50 atmospheres pressure andtemperatures from about 15 C. to about 180 C.

The process of the instant invention may be conducted either in thepresence, or absence of a solvent. When the monomer is in the vaporphase under selected temperature and pressure conditions, it is oftenpreferable to employ an inert liquid diluent which is free of ethylenicor acetylenic unsaturation. Such suitable solvents are those which areessentially unreactive with the catalyst or the catalyst components andwith unsaturated aliphatic and cycloaliphatic hydrocarbons. Exemplary ofsuch suitable unreactive solvents are, hexane, octane, cyclohexane,benzene, toluene, xylene, chlorobenzene, dioxane and tetrahydrofuran.

Monomers which will undergo homopolymerization by the practice of theprocess of the present invention are conjugated aliphatic dienes andepoxides. Exemplary of the conjugated aliphatic dienes which willhomopolymerize in accordance with the process of the present inventionare:

1,3-butadiene Isoprene Chloroprene 2,3-dimethyl-1,3 butadiene Z-ethyll,3-butadiene 1,3-pentadiene 2,4-hexadiene 4-methyl-1,3-hexadiene2,4-heptadiene 2,6-dimethyll ,3-heptadiene 7-methyl-2,4-octadiene1,3-decadiene Ethylene oxide Propylene oxide 1-chloro-2,3-epoxypropaneIsobutylene oxide 1,2-epoxybutane 2,3-epoxybutane 1,2-epoxycyclooctane1,2,3,4-diepoxybutane 1,2,4,5-diepoxycyclohexane1,2,5,6-diepoxycyclooctane Styrene oxide The class of epoxides which arepreferred in the practice of the process of the present invention are ofthe formula:

R-CH/- C H-R (Formula I) wherein R and R are selected from the groupconsisting of hydrogen and lower alkyl radicals.

A type of interpolymer which can be produced is the polymer formed bythe reaction of one or more conjugated aliphatic dienes and one or moremonoolefinic polymerizable monomers of the formula:

R2 CII1=C R3 (Formula II) wherein R is selected from the groupconsisting of hydrogen and hydrocarbyl radicals and R is selected fromthe group consising of hydrogen, hydrocarbyl, substituted hydrocarbyl,halogen, nitrile and wherein m is 0 or 1.

Compounds in which R and R are hydrogen or bydrocarbyl groups, representa preferred class of compounds of this formula. Examples of suchsuitable hydrocarbyl groups are aliphatic groups, such as methyl,propyl, butyl, isobutyl, 2-ethylhexyl and cyclohexyl and aromaticgroups, such as phenyl, tolyl and xylyl. Exemplary momomers of the aboveformula which are useful in the practice of the present invention are:

Ethylene Vinyl cyclohexene Propylene Styrene l-butene p-Chlorostyrenel-pentene Allylbenzene l-hexene Methyl styrene l-heptene Vinyl chloridel-octene Vinyl bromide Allyl alcohol Acrylonitrile 3-methoxypropeneAcrolein 3-ethyoxypropene Methacrolein S-hexene-Z-one Methylmethacrylate Allyl chloride Acrylic acid Methallyl chloride Methacrylicacid Allyl cyanide Methyl acrylate Vinyl cyclohexane Another type ofinterpolymer which can be produced is the polymer formed by the reactionof one or more conjugated aliphatic dienes and one or more epoxides.Interpolymers of this type have not previously been reported in theprior art. These monomers may be polymerized in any desired ratio. Forexample, sulfur curable interpolymers can be produced using as little asabout 1% by weight of 1,3-butadiene to as much as 90% by weight of1,3-butadiene or more. In addition to being sulfur curable these novelinterpolymers are elastomeric, resistant to oxidative attack and possessexcellent wear characteristics. Accordingly these types of polymers canreadily be used as a substitute for natural and known synthetic rubbersin many applications, such as automobile tires, weather stripping, etc.Exemplary of the conjugated aliphatic dienes which can enter into thisinterpolymerization are: 1,3-butadiene, isoprene, chloroprene,2,3-dimethyl-1,3-butadiene, 2-ethyl-l,3-butadiene, 1,3 -pentadiene,2,4-hexadiene, 4-methyl-1,3-hexadiene, 2,4-heptadiene, 2,6-dimethyl-1,3-heptadiene, 7-methyl-2,4-octadiene and 1,3- decadiene.Exemplary epoxides which will enter into interpolymerization reactionwith the conjugated aliphatic dienes are: Ethylene oxide Propylene oxide1-chloro-2,3-epoxypropane Isobutylene oxide 1 ,Z-epoxybutane2,3-epoxybutane 1,2-epoxycyclooctane 1,2,3,4-diepoxybutane1,2,4,5-diepoxycyclohexane 1,2,5 ,6-diepoxycyclooctane Styrene oxide Theclass of epoxides which are preferred in the practice of the process ofthe present invention are of the formula:

0 R-CH CH-R (Formula I) wherein R and R are selected from the groupconsisting of hydrogen and lower alkyl radicals.

By the practice of the process of the instant invention other types ofinterpolymers may be produced in addition to the interpolymers discussedabove, as will be obvious to one skilled in the art. Interpolymers oftwo or more conjugated dienes may be prepared, such as an interpolymerof 1,3-butadiene and isoprene, as well as interpolymers of two or moreepoxides, such as an interpolymer of ethylene oxide and propylene oxide.Another interpolymer which can be prepared is an acrylonitrile, 1,3-butadiene, a-methyl styrene terpolymer. Also, an ethylene, propylene,isoprene terpolymer can be prepared.

The catalyst compositions which may be employed in the practice of theprocess of the present invention are admixture products of (a) an iron(III) compound, (b) a hydrocarbyl, hydrocarboxy or hydride compound ofaluminum, and (c) a phosphorus ester having at least one phosphinichydrogen atom.

Catalytic compositinos which may be employed in the practice of theprocess of the present invention can be prepared from any iron (III)compound. Illustrative of such iron (III) inorganic compounds are:ferric fluoride, ferric iodide, ferric bromide, ferric chloride, ferricoxide, ferric hydroxide, ferric hypophosphite, ferric orthophosphate,feric thiocynate, ferric ferricyanide, ammonium ferricyanide, potassiumferric sulphate and others. Examples of iron (III) organic compoundswhich can be used in the practice of the process of the presentinvention include salts of acetic, propionic, hexanoic, ethyl hexanoic,oleic, stearic, oxalic, suberic, benzoic, trimellitic, citric, lactic,and tall oil acids, as well as ferric derivatives of alcohols, ketones,aldehydes and nitrogen containing organics such as benzoylacetone,dimethylglyoxime, 8- hydroxy quinoline, glycine,nitrosophenylhydroxylamine, etc., and complexes of organic moleculeswith inorganic ferric salts, such as tetrapyridine ferric chloride. Froma practical viewpoint, however, it is often desirable to prepare thecatalysts in solvent for one or more of the components. The use of suchsolvents, which are described in detail below, generally facilitates therapid interaction and high utilization of the components, factors whichare of the utmost importance in commercial applications. Iron (III)compounds which have a significant solubility in said solvents aretherefore highly desirable and represent a preferred source of the heavymetal component. Such preferred iron (III) sources include the ferrichalides, such as ferric chloride; ferric salts of monobasic carboxylicacids, preferably having at least six carbon atoms, such as ferricnaphthenate; and ferric chelates in which the organic chelating group isbonded to the iron with both conventional and coordination bonds, suchas ferric acetyl acetonate.

The aluminum containing component of the catalyst employed in thepractice of the process of the present invention may be any hydrocarbyl,hydrocarboxy or hydride compound of aluminum. Illustrative of suchcompounds are: trimethyl aluminum, triisobutyl aluminum, trioctylaluminum, tridodecyl aluminum, tricyclohexyl aluminum, triphenylaluminum, tritolyl aluminum, phenyoxydiethyl aluminum, diethyoxyethylaluminum, isobutyl aluminum dihydride, aluminum hydride and diethylphenyl aluminum. A preferred class of aluminum containing components isrepresented by the general formula:

(Formula III) wherein R is an alkyl radical and A is selected from thegroup consisting of alkyl, lower alkoxy and hydride radicals. Examplesof such preferred compounds include tri(polyethylene) aluminum compoundsin which each polyethylene group contains from about six to about thirtycarbon atoms, ethoxydiethyl aluminum and diethyl aluminum hydride. Alkylaluminum compounds such as triethyl aluminum and triisobutyl aluminumrepresent an especially preferred embodiment for use in the practice ofthe process of the present invention.

The phosphorus esters which have been found to be suitable for use ascomponents of the catalyst compositions in the practice of the processof the present invention are those having at least one phosphinichydrogen atom; i.e., esters having at least one hydrogen atom bondeddirectly to phosphorus, or tautomers thereof. Suitable esters of thistype can be represented by the general formula:

(Formula IV) wherein Z is selected from the group consisting of H, R andOH radicals, R is selected from the group consisting of hydrocarbyl,substituted hydrocarbyl, hydrocarboxy and substituted hydrocarboxyradicals and n is from 0 to 1 inclusive. Illustrative of such suitableesters are the following compounds:

Dimethyl hydrogen phosphite Diallyl hydrogen phosphite Dioctyl hydrogenphosp'hite Didodecyl hydrogen phosphite Dibenzyl hydrogen phosphiteDicyclohexyl hydrogen phosphite Di(p-anet'hylphenyl) hydrogen phosphitePhenyl isobutyl hydrogen phosphite Di(2-phenylethyl)hydrogen phosphiteDi(2methoxyethyl) hydrogen phosphite Di(p-chlorophenyl)hydrogenphosphite Di(2-methoxyphenyl)hydrogen phosphite Methyl dihydrogenphosphite Isopropyl dihydrogen phosphite Z-ethyl hexyl dihydrogenphosphite Cyclohexyl dihydrogen phosphite Phenyl dihydrogen phosphitep-chlorophenyl dihydrogen phosphite Z-methoxyphenyl dihydrogen phosphiteDimethyl phosphine Diphenyl phosphine Methyl phosphine oxide Phenylphosphine oxide Dimethyl phosphine oxide Diphenyl phosphine oxide Methylhydrogen phosphonite Dodecyl hydrogen phosphonite Phenyl hydrogenphosphonite Methyl phosphinic acid Z-ethylhexyl phosphinic acid Benzylphosphinic acid Phenyl phosphinic acid p-Methylphenyl phosphinic acidp-Chlorophenyl phosphinic acid Many of these esters are known to existas trivalent or pentavalent phosphor-us tautomers, either of which canbe used as a component of the catalyst compositions employed in thepractice of the process of the present invention. The nomenclature usedabove, while strictly applicable only to a single tautomer, is commonlyapplied to either tautomeric form and is so intended as used herein. Forexample, the name, methyl dihydrogen phosphite, while strictlyapplicable only to the structure:

H 0 (Formula V) 6 is, as used herein, intended to be inclusive of eitherthis structure or its pentavalent phosphorus tautomer:

CHaO H HO/ \O (Formula VI) as well as mixtures thereof. Similarly, itshould be understood that the name methyl hydrogen phosphonate, which isstrictly descriptive only of the pentavalent phosphorus tautomer, is tobe given its common meaning, which encompasses both tautomeric forms.

Preferred groups of phosphorus esters are those which can be representedby the formula:

i R \O (Formula VII) and HO (Formula VIII) wherein R has the samemeaning as set forth above. 'Esters of Formulae VII and VIII in which Ris a hydrocarboxy radical have been found to be especially suitablecatalyst components. Typical of these unusually effective esters arephenyl phosphinic acid, phenyl dihydrogen phosphite,di(2-ethylhexyl)hydrogen phosphite and diphenyl hydrogen phosphite.

It has been found that the ratio of the components of catalysts used inthe practice of the process of the present invention may be varied overa wide range. A catalytically active composition can be produced with amolar ratio of iron to aluminum in the components of from about 1:0.1 toabout 1:25 or higher. Similarly, the molar ratio of iron to phosphorusmay be varied from 120.1 to about 1:25 and higher. Molar ratios outsidethese ranges can be used; however, there is no apparent advantage inusing very large excesses of any component. In general, it is preferredto utilize a molar ratio of iron to aluminum of from about 1:05 to about1:10 and an iron to phosphorus ratio of from about 1:05 to about 1:8.

The order of addition of the catalyst components is not critical;however, with regard to the polymerization of the epoxides, it ispreferred to form the catalyst in the presence of the epoxide. Theadmixture of components may be effected either in the presence orabsence of a solvent medium. It generally 'has 'been found, however,that the interaction of the components is facilitated by effecting theadmixture in the presence of an inert solvent medium. Examples of suchinert solvents include aromatic and aliphatic hydrocarbons which arefree of ethylenic or acetylenic unsaturation, such as, benzene, toluene,xylene, isooctane, normal hexane and liquid propane, or saturated cyclicethers such as, tetrahydrofuran and 1,4- dioxane. Ring substitutedhalogenated aromatics, such as chlorobenzene and p-chlorotoluenelikewise can be satisfactorily utilized as inert solvents.Alternatively, the catalyst compositions may be formed in situ in apolymerization system, in which case the unreacted monomer or liquidpolymer may serve as a solvent.

The catalyst compositions employed in the practice of the process of thepresent invention may be produced by admixing the components over a widetemperature range. Catalytic compositions can be obtained attemperatures above 300 C. and below --30 C.; however, it is seldomdesirable or necessary to utilize temperatures outside the preferredrange of from about 0 C. to about C. The interaction of the componentsis generally extremely rapid and often is accompanied by a color change.Because of this rapid interaction and the stability of the product overa wide temperature range, the catalysts employed in the practice of theprocess of the present invention may be preformed and stored forsubstantial periods before being used in a polymerization reaction orthey may 'be formed in the presence of the polymerizable monomers underconventional polymerization conditions.

Although these catalytic compositions are simple to prepare and aregenerally quite stable and insensitive to most extraneous materials, theincorporation therein of an aluminum hydrocarbyl or hydride requiresthat precautions be taken to isolate both the components and theinteraction product from excessive quantities of water, oxygen, alcohol,carbon dioxide and other materials which are known to be reactive withthese aluminum compounds. Small quantities of such reactive impuritiesare, of course, tolerable, however, it is preferred that they beessentially excluded in order to achieve maximum effectiveness of thesecatalyst compositions.

A more comprehensive understanding of the invention may be obtained byreferring to the following illustrative examples which are not intended,however, to be unduly limitative.

EXAMPLE I A clean dry magnetically stirred 300 milliliter autoclave isflushed with argon for five minutes and then charged with fiftymilliliters of benzene, 0.25 gram (0.7 millimole) of ferricacetylacetonate, 0.3 gram (1.0 millimole) of di(2-ethylhexyl)hydrogenphosphite and 3 milliliters (4.5 millimoles) of a 20% by weight solutionof triethyl aluminum in benzene. After stirring the autoclave at roomtemperature for five minutes, 31 grams (0.705 mole) of ethylene oxide ispressured into the autoclave and the temperature raised to 100 C.Stirring is continued at 100 C., plus or minus 5 C., for four andone-half hours. The autoclave is then vented and the catalystdeactivated by the addition of milliliters of methanol. The solution isthen stripped of solvent in a rotary evaporator at 100 C. under vacuum.The 17 grams of tough polymer film remaining represents a 55% conversionof ethylene oxide. Infrared analysis shows the product to be a typicalpolyether.

EXAMPLE II EXAMPLE III The procedure of Example II is conducted at atemperature of 120 C. for a period of three hours. A 24% yield of toughpolymer is recovered.

EXAMPLE IV To a clean dry argon filled flask are added 0.25 gram offerric acetyl acetonate, 0.5 grams of di(Z-ethylhexyl) hydrogenphosphite, 3 milliliters of a 20% by weight solution of triethylaluminum in toluene and 50 milliliters of toluene. After storing thesealed flask for 24 hours, its entire contents are introduced into a 500milliliter magnetically stirred autoclave containing 34 grams of1,3-butadiene and grams of propylene oxide. Heating of the autoclave to70 C. with vigorous stirring initiates a highly exothermic reaction.External heating is then withdrawn and the autoclave cooled so as tomaintain the temperature of its contents below 145 C. and the pressureto less than 200 p.s.i.g. After 37 minutes, the autoclave is vented andthe resulting polymer coagulated with 20 milliliters of methanol. Thecoagulated product is dried under vacuum to yield 34 grams of toughresilient polymer which is shown by infrared analysis to contain etheroxygen and an 8% cis, 7% trans and 85% vinyl olefin structure.

EXAMPLE V The procedure of Example IV is repeated with 40 grams of1,3-butadiene and 20 grams of ethylene oxide.

The reaction is maintained at 70 C. for three hours to yield 32 grams oftough interpolymer having a vinyl content of EXAMPLE VI A clean drymagnetically stirred 300 milliliter autoclave is flushed with nitrogenand charged with 0.3 mole of 1,3-butadiene, 0.88 mole of propylene, 0.7millimole of ferric naphthenate and 2.8 millimoles of di(2-ethylhexyl)-hydrogen phosphite. Stirring and gentle heating is then commenced and 5milliliters of a 20% solution of triisobutyl aluminum in toluene isintroduced. The reaction temperature is maintained at C. for two hours,at the end of which time, the autoclave is cooled and vented and thecatalyst deactivated by the addition of 25 milliliters of 50% by volumeaqueous methanol. The precipitated product is dried under vacuum toyield 19 grams of a tough interpolymer polymer having a cisztranswinylratio of 13% 14% 273% and a methylene to methyl group ratio of 4:1.

EXAMPLE VII The general procedure of Example VI is utilized topolymerize 28 grams of 1,3-butadiene with 40 grams of acrylonitrile atC. After four hours at this temperature, the catalyst is deactivated asin Example VI and the entire reactor contents is then introduced intomilliliters of normal hexane. The precipitated material is then removedfrom the hexane and dried under vacuum to yield five grams ofinterpolymer having a cisztranszvinyl ratio of 2l%:73%:6%.

EXAMPLE VIII The general procedure of Example VI is used to cause rapidpolymerization at 30 C. to 50 C. of 36 grams of 1,3-butadiene and 12grams of ethylene.

EXAMPLE IX A clean dry magnetically stirred 500 milliliter autoclave isflushed with argon for five minutes and charged with 50 milliliters ofbenzene, 0.7 millimole of ferric chloride, 2.1 millimoles of phenylphosphinic acid and 5 milliliters of a 20% by weight solution oftriethyl aluminum in toluene. The autoclave contents are stirred at roomtemerature for ten minutes followed by addition of 30 grams ofacrylonitrile, 58 grams of styrene and 20 grams of 1,3- butadiene. Afterstirring the resulting solution at 100 C. for seven hours, the autoclaveis vented and 25 milliliters of methanol added. Separation and drying ofthe precipitate yields 32 grams of tough hard interpolymer which, uponheating at 200 C. for one hour, gives a clear very hard resin film.

EXAMPLES X THROUGH XIII The procedure of Example IX is repeated varyingthe mole ratio of the monomers charged as shown below:

styrene in charge styrene in inter- 200 C. for 1 hr.) polymer product X1:1:1 34:31:35 Flexible, creases. AI 1:2:1 44:36:20 Very flexible,

does not crease. XII 1:122 20:24:56 Brittle, breaks 7 when bent. XIII1:0. 5 1 35:24:41 Very flexible,

does not crease.

EXAMPLE XIV lution at 100 C. for two hours, the autoclave is vented andthe catalyst deactivated by the addition of 25 milliliters of 50% byvolume aqueous methanol. The precipi- ,tated product is dried undervacuum to yield grams of a tough hard interpolymer having acisztranszvinyl ratio of 24% 10% 166% respectively.

EXAMPLE XV A clean dry magnetic-ally stirred 500 milliliter autoclave isflushed with nitrogen for five minutes and charged with 0.7 millimole offerric acetyl acetonate, 0.7 millimole of triphenyl phosphite, 5Omilliliters of dry benzene and 5 milliliters of a by weight solution oftriethyl aluminum in benzene. After stirring for five minutes, 56 gramsof 1,3-butadiene is introduced. The autoclave is then heated to 100 C.and held at that temperature for 1 hour, following which, unreactedgases are vented and 25 milliliters of methanol added to deactivate thecatalyst. Evaporation of the solvents and liquid butadiene oligomersyields a trace of solid polymer.

EXAMPLE XVI The process of Example XV is repeated utilizing 0.7millimole of disphenyl hydrogen phosphite in place .of triphenylphosphite. The exothermic nature of the reaction necessitates cooling ofthe autoclave so as to prevent the temperature from exceeding 100 C.Twelve minutes after the initiation of the reaction, the autoclave isvented and the reaction mixture worked up as in Example XV, yielding 55grams of solid polymer having a cisztrans: vinyl ratio of 10% :6% :84%.

EXAMPLE XVII To a clean dry argon filled flask are added 0.2 gram offerric acetyl acetonate, 0.5 gram of di(p-tolyl)hydrogen phosphite and 5milliliters of a 20% by weight solution of triethyl aluminum in benzene.The sealed flask is shaken gently for ten minutes and its entirecontents is then introduced into a 300 milliliter magnetically stirredautoclave containing 50 milliliters of dry benzene. Stirring is begun as50 grams of 1,3-butadiene is introduced. The autoclave is then heated toC. to C., at which temperature, a vigorous exothermic reaction initiatesand proceeds, in the absence of additional external heating, to amaximum of 175 C. Deactivation of the catalyst with milliliters ofaqueous phosphoric acid, separation of the aqueous phase and evaporationof the solvents yields 50 grams of a tough, highly cross-linked 1,2-polymer.

I claim:

1. Process for polymerizing at least one monomer selected from the groupconsisting of conjugated aliphatic dienes having up to 12 carbon atomsand lower 1,2-alkylene oxides comprising contacting said monomer with acatalyst consisting essentially of:

(a) a hydrocrabon soluble iron (III) compound,

(b) an aluminum compound selected from the group consisting ofhydrocarbyl and hydride compounds of aluminum, and

(c) a phosphorus ester having at least one phosphinic hydrogen atom.

2. The process of claim 1 wherein said aluminum compound is of theformula:

(R Al-A ,is of the formula:

wherein Z is selected from the group consisting of H, R and OH radicals,R is selected from the group consisting of hydrocarbyl, substitutedhydrocarbyl, hy'drocarboxy and substituted hydrocarboxy radicals havingl-12 carbon atoms, and n is from 0 to l inclusive.

5. The process of claim 4 wherein said phosphorus ester is of theformula:

6. The process of claim 1 wherein said iron (III) compound is selectedfrom the group consisting of ferric salts of halogen and carboxylicacids and ferric chelates.

7. The process of claim 6 wherein said iron (III) compound is ferricacetylacetonate.

8. The process of claim 1 wherein said monomer is 1,3-butadiene.

9. The process of claim 1 wherein said! monomer is a lower 1,2-alkyleneoxide.

10. Process for the production of an interpolymer of 1,3-butadiene withat least one lower 1,2-alkylene oxide comprising contacting an admixtureof said butadiene and said alkylene oxide at a temperature of from about30 C. to about 300 C. with a catalyst composition consisting essentiallyof:

(a) an iron (III) compound selected from the group consisting of ferricsalts of monocarboxylic acids and ferric chelates,

(b) a trihydrocarbyl aluminum, and

(c) a phosphorus ester of the formula:

' wherein Z is selected from the group consisting of H, R

and OH radicals, R is selected from the group consisting of C C ofhydrocarbyl, substituted hydrocarbyl, hydrocarboxy and substitutedhydrocarboxy radicals, and n is from 0 to 1 inclusive, and the molarproportions of iron, aluminum and phosphorus in said components being1:0.1 to 1:25:25.

11. The process of claim 10 wherein said alkylene oxide is ethyleneoxide.

12. The process of claim 10 wherei nsaid alkylene ovide is propyleneoxide.

13. Process for the production of an interpolymer of 1,3-butadiene andat least one additional polymerizable monomer of the formula:

R2 CHFC/ wherein R is selected from the group consisting of hydrogen andhydrocarbyl and R is selected from the group consisting of hydrogen,hydrocarbyl, substituted hydrocarbyl, halogen, nitrile and wherein Z isselected from the group consisting of H, R and OH radicals, R isselected from the group consisting of C C hydrocarbyl, substitutedhydrocarbyl, hydrocarboxy and substituted hydrocarboxy radicals, and nis from 0 to 1 inclusive, and the molar proportions of iron, aluminumand phosphorus in said components being 1:0.l:0.1 to 1:25:25.

14. The process of claim 13 wherein said additional polymerizablemonomer is ethylene.

15. The process of claim 13 wherein said additional polymerizablemonomer is propylene.

16. The process of claim 13 wherein said additional polymerizablemonomer is acrylonitrile.

17. An elastomeric interpolymer of at least one conjugated aliphaticdiene and at least one lower alkylene oxide produced by the method ofclaim 10.

19. An elastomeric interpolymer of L'S-butadiene and propylene oxideproduced by the method of claim 10.

References Cited UNITED STATES PATENTS 2,977,350 3/1961 Fasce et a1.26094.9 3,077,467 2/1963 Gurgiolo 2602 3,159,607 12/1964 DAlelio260--94.3 3,240,747 3/ 1966 Heitmiller et a1. 26094.9

WILLIAM H. SHORT, Primary Examiner.

T. PERTILLA, Assistant Examiner.

US. Cl. X.R.

18. An elastomeric interpolymer of 1,3-butadiene and 15 260 943 825 83 5841 85 3 252 428 429 430 ethylene oxide produced by the method of claim10.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,419,505 December 31, 1968 William E. Marsico It is certified thaterror appears in the above identified patent and that said LettersPatent are hereby corrected as shown below:

Column 1, line 32, cancel "now U. S. Patent No. 3,340,489";

Column 4, line 26,

line 36, "art" should read are "compositinos" should read compositionsline 32,

"feric" should read ferric Column 9, line 23, "disphenyl" Column 10,line 44, "wherei nsaid should read diphenyl alkylene ovide" should readwherein said alkylene oxide Signed and sealed this 9th day of December1969,

(SEAL) Attest:

WILLIAM E. SCHUYLER, JR.

Edward M. Fletcher, Jr.

Commissioner of Patents Attesting Officer

